CN103436095B - Ultraviolet-curing water-based inkjet ink - Google Patents
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Abstract
The invention discloses ultraviolet-curing water-based inkjet ink. The ultraviolet-curing water-based inkjet ink at least comprises the following components in percentage by weight: 1%-12% of nanometer pigment/water-soluble pigment, 1%-5% of dispersing agent, 1%-15% of UV (Ultraviolet)-curing modified polyurethane resin emulsion (solid content), 1%-10% of photoinitiators, 20%-50% of reactive diluents, 5%-25% of humectants, 5%-15% of penetrating agents, 0%-2% of surfactants, 0%-2% of pH regulators, 0.1%-0.5% of sterilization preservative, and the balance of deionized water. The ultraviolet-curing water-based inkjet ink is characterized in that the ink has excellent storage stability and printing fluency; the ink has excellent performances including water resistance, light resistance, solvent resistance, scratch resistance, ageing resistance, high-low temperature resistance, high brightness, good adhesive strength and quick curing speed, is suitable for various printers to print various uncoated and nonprinting coating media, hydrophobic and oily media, and is wide in application area.
Description
Technical field
The present invention relates to a kind of ink for ink-jet print, be specifically related to the water based ink jet ink that a kind of UV solidifies.
Background technology
Spray ink Printing, due to powerful advantages, by the development of nearly 30 years, has had marked improvement, has been used in the fields such as digital printing, digit printing, digital image, office docuemts, outdoor air brushing, surface decoration, has provided convenience to human being's production and life.Water based ink jet ink is with environmental protection, and the scope of application is wide, is subject to people's favor.
Along with the increase of use and the expansion of scope, find the shortcoming of water based ink jet ink.Such as printer down time is slightly of a specified duration, easily blocks shower nozzle; In paper ink not scuff draw, lackluster, color and luster is dim; Enamelled paper, plastics, glass etc. can not be printed; Hydrophobicity and oil medium can not be printed; Paper needs special coating to adapt to; Printout is placed on for some time in water and acid-base reagent, and trace occurs fuzzy; Be printed on trace on milk box to come off through high temperature steaming.A lot of printed document can with spray ink Printing because ink for ink-jet print performance limit, and such as office docuemts people select Laser Printing, and printed form selected by packaging, plastics, glass etc.Therefore the needs that the performance improving water based ink jet ink is produced to adapt to people and lived are needed especially.Specifically 1. ink for ink-jet print storage stability and print fluency; 2. the over-all propertieies such as the water tolerance photostabilization rub resistance height bright property ageing resistance cementability of ink for ink-jet print are improved; 3. fast dry, improve print speed; 4. expand the use range of ink for ink-jet print, such as, print without coating and non-print coating media, hydrophobicity and oil medium.
Traditional ink for ink-jet print drying has infiltration drying, volatile dry, crosslinking curing is dry, UV radiation curing is dry, hydrophobicity and oil medium are permeated drying be difficult to carry out, the drying of selection crosslinking curing, UV radiation curing dried forms make ink for ink-jet print rapid drying.Traditional UV radiation curing is dry, and owing to adding a large amount of reactive thinners and photosensitive prepolymer in ink, the viscosity of ink for ink-jet print is higher, can not adapt to some printer, such as office and household printer.
Summary of the invention
The object of this invention is to provide a kind of ink for ink-jet print, there is excellent storage stability and print fluency, there is the over-all propertieies such as water tolerance photostabilization rub resistance height bright property ageing resistance cementability, fast dry, print without coating and non-print coating media, hydrophobicity and oil medium.
Another object of the present invention is to provide the preparation method of ink for ink-jet print of the present invention.
Technical scheme of the present invention is: a kind of water based ink jet ink of UV solidification, and weight percent meter has component at least:
Nano dye 1-12%,
Dispersion agent 1-5%,
Modified polyurethane resin emulsion (solid content) 1-15% of UV solidification,
Light trigger 1-10%,
Reactive thinner 20-50%,
Wetting Agent for Printing Inks 5-25%,
Permeate agent 5-15%,
Tensio-active agent 0-2%,
PH conditioning agent 0-2%,
Fungicidal preservative 0.1-0.5%,
Balance deionized water.
As preferably: the modified polyurethane resin emulsion of described UV solidification is selected from: at least one in epoxy resin-polyurethane resin emulsion, epoxy resin and acrylic ester-ester-polyurethane resin emulsion, Viscotrol C-acrylate-polyurethane resin emulsion, acrylate-polyurethane resin emulsion, organic silicon-acrylate-ester-polyurethane resin emulsion, polyester-urethane resin emulsion, polyether-polyurethane resin emulsion, polyurea-polyuretahne resin emulsion etc.; Particle diameter <100 nanometer, 24 hours water-intake rate≤10% after film forming; Emulsion appearance is as clear as crystal-blue light or yellowish translucent liquid, and second-order transition temperature-50-120 DEG C, viscosity <800 centipoise is even low to moderate 50 centipoises, and soft durometer is adjustable, and preservation period reaches 2 years, all-transparent after film forming.Meanwhile, the undersaturated reactive group that these resin emulsions can react in addition, can be excited by UV quantity of radiant energy and react, and is applicable to making the component that UV solidifies water based ink jet ink.
As preferably: described dispersion agent is organic high molecular polymer.Described organic high molecular polymer is at least one in BYK-2163, BYK-2164, BYK-180, BYK184, BYK-190, BYK2012, BYK-2020 dispersion agent of Bi Ke chemistry.
As preferably: nano dye is selected from nano metal colour lustre pigments: metallic copper, metallic aluminium, metallic zinc, metallic tin etc.; Mineral dye selective oxidation iron oxide red, iron oxide yellow, group's indigo plant, carbon black, Rutile type Titanium Dioxide etc.; Pigment dyestuff is selected: red C.I. Pigment Red 112,122,188,184,179; Yellow: C.I. pigment yellow 17,83,14 etc.; Blue: C.I. pigment Blue 15: 3,56,60,63 etc.; Orange: C.T. pigment Orange 13; Green: C.I. pigment Green 7; Purple: at least one in C.I. pigment violet 1,23 etc.
As preferably: the preferred light fastness of water-soluble dye 6 grades and above water-soluble dye; Dispersion agent is not used when making tinting material with water-soluble dye; Such as have: the direct Huang 132 of C.I., C.I. be Huang 86, C.I. directly Huang 17, C.I. Reactive Red 23, C.I. direct yellow 142 directly; The water-soluble metal complex dyestuff of commercially available light fastness 6-7 level and alcohol water two solube metallic complex dyestuff, have C.I. solvent yellow 21, C.I. solvent red 8,122, C.I. solvent blue 70, the water-soluble metal complex dyestuff of C.I. solvent black 27,55,34 modification and alcohol water two solube metallic complex dyestuff; There is C.I. directly Huang 106, C.I. directly red 80, C.I. direct black 166 (direct black N-BN), C.I. directly blue 106 (the gorgeous blue FF2GL of direct sun-proof), C.I. directly blue 108 (direct fast blue FFRL), at least one in C.I. Xylene Red 336 grade.
As preferably: described light trigger is bitter almond oil camphor and derivative (st-yrax, benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether), benzil class (diphenylethan, α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone), alkylbenzene ketone (α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones), acyl group phosphorous oxides (aroyl phosphine oxide, two benzoylphenyl phosphine oxide), benzophenone (benzophenone, 2, 4-dihydroxy benaophenonel, Michler's keton), thioxanthones (sulfo-propoxy-thioxanthone, isopropyl thioxanthone), dibenzoyl, salicylate class, group-substituted acrylonitrile, triazines, two or more light trigger is composite arbitrarily for hindered aminess etc.
As preferably: reactive thinner is hydroxyethyl methacrylic acid, vinylformic acid lauryl alcohol fat, vinylformic acid stearyl alcohol fat, hexanediyl ester, triethylene glycol diacrylate, O-phthalic acid diethylene glycol diacrylate fat, diethylene glycol diacrylate, neopentylglycol diacrylate, tripropylene glycol diacrylate, Viscoat 295, pentaerythritol triacrylate etc., single, double, polyfunctionality reactive thinner is composite with 3-6:0-4:0-1.
As preferably: at least one in the modified polyurethane resin emulsion of UV solidification also in the composite epoxy-acrylics emulsion, organosilicon modified crylic acid resin emulsion, organic fluorine modified acrylic resin emulsion, organic silicon-fluorine modified acrylic resin emulsion etc. having UV to solidify.
As preferably: wetting Agent for Printing Inks can select the raw material of safety non-toxic.The alcohols such as such as Virahol, ethanol, isopropylcarbinol; The polyalcohols such as glycol ether, propylene glycol, butyleneglycol, triglycol, Tetraglycol 99, polyoxyethylene glycol, polypropylene glycol, glycerine, 1,2-PD, BDO, 1,3-PD, BDO, 1,3-PD, 1,2-hexylene glycol.
As preferably: permeate agent is selected from: diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propandiol butyl ether, propylene glycol isobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, the only butyl ether of Diethylene Glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, TRIGLYME, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetraethyleneglycol dimethyl ether, TEG diethyl ether, monoethylene glycol and polyoxyethylene glycol phenyl ether, MPG and polypropylene glycol phenyl ether, 2-Pyrrolidone, METHYLPYRROLIDONE etc.
As preferably: tensio-active agent selects BYK-345, BYK-348 of Bi Ke chemical company.
As preferably: above-mentioned PH conditioning agent, select the raw material of safety non-toxic.PH conditioning agent is selected from citric acid, Tripotassium Citrate, lactic acid, oxysuccinic acid, Trisodium Citrate, hydrochloric acid, Potassium Hydrogen Phthalate, potassium hydroxide, sodium hydroxide, quaternary ammonium hydroxide, such as tetramethyl-ammonium; Carbonate: such as salt of wormwood, sodium carbonate, Quilonum Retard; Phosphoric acid salt; METHYLPYRROLIDONE; Ethamine, diethanolamine, trolamine, ammoniacal liquor etc.
As preferably: anticorrosion and bactericidal agent selects the raw material of safety and environmental protection.Such as sodium sorbate, potassium sorbate, isothiazolinone, BIT class etc.
As preferably: the auxiliary agent improving ink performance can be added, as viscosity modifier, conductivity adjustment agent, stablizer, intercalating agent, defoamer, coupling agent, flow agent, thinner etc.
Preparation method of the present invention:
(1) prepare each component of ink, stir, grinding machinery speed lapping (500-3000 rev/min) 1-3 hour, record particulate D90≤120 nanometer in ink mixture, obtain ink mixture.
(2) ink mixture leaves standstill slaking in-7 days in 12 hours.
(3) the every physical and chemical index of ink mixture is detected according to QB/T2730.1-2005, QB/T 2730.2-2005.
(4) with 1 micron, 0.45 micron, 0.22 micron membrane filter filtration, finished product is obtained.
The application of the water based ink jet ink of UV solidification, is printed on various without on coating media and non-print coating media, hydrophobicity and oil medium, solidifies while printing with UV.
Beneficial effect of the present invention and advantage are:
1: ink storage stability is good, print fluency good.
2: ink chromatogram is complete, nano_scale particle.
3: improve the over-all propertieies such as ink photostabilization water tolerance chemical resistant properties resistant of high or low temperature rub resistance height bright property ageing resistance.
4: adapt to without coating and non-print coating media, hydrophobicity and oil medium, be applied to the fields such as digital printing, digit printing, digital image, office docuemts, outdoor air brushing, ceramic tile wallpaper, glass plastic, surface decoration.
5: select UV-light (UV) to solidify, expand ink range of application, accelerate time of drying and the print speed of ink.
6: ink advantages of nontoxic raw materials, prepare and make apparatus environmental protection property.Nonpoisonous and tasteless when printing.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.
The formula of ink:
Preparation method: see " preparation method of the present invention " in " summary of the invention ":
Table 1: the formula () of ink
Table 2: the formula (two) of ink:
Embodiment 15-embodiment 22: embodiment and comparative example stability of ink and intermittent printing effect, print fluency and detect:
According to national QB/T2730.1-2005, QB/T 2730.2-2005 standard detection
The ink of preparation is loaded in Epson me1+ ink-cases of printers, be printed on common print paper.
Table 3: the stability of embodiment and comparative example ink and intermittent printing effect, printing fluency
Embodiment 23-embodiment 30: the ink of embodiment and comparing of comparative example ink performance:
The ink of preparation is loaded in Epson me1+ ink-cases of printers, be printed on common print paper.
According to national QB/T2730.1-2005, QB/T 2730.2-2005, QB/T2603-2007, GB/T13217.2-2009 standard detection
Water tolerance detects:
Detection method: intercept one section, diffusibleness classification handwriting test paper, flood in deionized water, observe ink and fade and diffusion time, and record.Flood in deionized water after 24h, take out seasoning, and with contrasting colour mark ready visual contrast.
Resistance to salt acidic detection:
Detection method: intercept one section, diffusibleness classification handwriting test paper, flood 24h in 10% (volume ratio) aqueous hydrochloric acid after, flood 10min in deionized water, take out seasoning, and with contrasting colour mark ready visual contrast.
Resistance to alcohol repellency detection:
Detection method: intercept one section, diffusibleness classification handwriting test paper, after flooding 10min, takes out seasoning in 50% (volume ratio) aqueous ethanolic solution, and with contrasting colour mark ready visual contrast.
Resistant to ammonia water-based detects:
Detection method: intercept one section, diffusibleness classification handwriting test paper, flood 24h in 10% (mass percent) ammonia soln after, flood 10min in deionized water, take out seasoning, and with contrasting colour mark ready visual contrast.
The photostabilization of ink detects:
Detection method: get special two, the high light printing paper of air brushing, the assorted color lump of 30m mX30mm is gone out with 720dpiX 720dpi resolution printing, color lump and blue wool standard are installed simultaneously and are suspended in draughty test box, tan by the sun under ammonia arc lamp (blackboard temperature is no more than 45 DEG C), take out after 44h, according to the change rank of blue wool standard, evaluate sample.
The high thermal resistance of ink detects:
Detection method: intercept one section, diffusibleness classification handwriting test paper, be placed in the 100 DEG C of boiling water boiled, take out after dipping boils 5min, seasoning, and with contrasting colour mark ready visual contrast.
Ink lower temperature resistance detects:
Detection method: tested ink is poured in cold-resistant packing bottle, takes out after putting into (-20 ± 1) DEG C cryostat to 24h, after returning to room temperature, detects its print performance.
The rub resistance of ink detects:
Detection method: after treating that ink is bone dry, to rub same number with coin on two kinds of ink markss, until there is a kind of writing to occur abrasion mark, and record Rubbing number.By the strength generally scratched, the angle in coin and 45 degree, word table face is scratched back and forth on the surface of word, until there is a kind of writing surface to occur scratching vestige, record scratches number of times, determines and compares ink of the present invention and commercially available ink rub resistance.
High bright property, the ageing resistance of ink detect:
Detection method: by embodiment and comparative example ink under identical experiment environment, by range estimation, compares mutually and reaches a conclusion.
Table 4: embodiment of the present invention ink and comparative example ink performance comparison sheet:
Embodiment 31-embodiment 38: ink on a variety of media print performance detects
Detection method: the embodiment ink of preparation and comparative example ink are loaded in Epson me1+ ink-cases of printers, is printed on various media as described below, observe printing effect.
In table: it is clear that A represents trace, effective.B: represent trace fuzzy, weak effect `.C: represent seriously fuzzy, can not trace be seen clearly.
Table 5: ink various without the printing effect on coating media and non-print coating media
| Ink is selected | Lamp house cloth | Lantern slide | Plastic cloth | Enamelled paper | Tobacco and wine wrapping paper | Cloth | Waterproof cloth | |
| Embodiment 31 | Embodiment 4 | A | A | A | A | A | A | A |
| Embodiment 32 | Embodiment 5 | A | A | A | A | A | A | A |
| Embodiment 33 | Embodiment 6 | A | A | A | A | A | A | A |
| Embodiment 34 | Embodiment 7 | A | A | A | A | A | A | A |
| Embodiment 35 | Comparative example 1 | B | C | C | B | B | B | C |
| Embodiment 36 | Comparative example 2 | B | C | C | B | B | B | C |
| Embodiment 37 | Comparative example 3 | B | C | C | B | B | B | C |
| Embodiment 38 | Comparative example 4 | B | C | C | B | B | B | C |
Embodiment 39-embodiment 46: embodiment of the present invention UV ink and comparative example ink cured velocity measuring
Detection method: embodiment 4,5,6,7 ink of preparation is loaded in rowland LED-330UV ink-cases of printers, be printed on common print paper, use UV light irradiation immediately during printing.Comparative example 1,2,3,4 ink of preparation is loaded in Epson me1+ ink-cases of printers, be printed on common print paper.Print identical content.
Table 6: embodiment UV ink and comparative example ink cured velocity ratio comparatively:
Claims (9)
1. the water based ink jet ink of a UV solidification, weight percent meter has component at least: nano dye 1-12%, and the modified polyurethane resin emulsion of dispersion agent 1-5%, UV solidification is in solid content 1-15%, light trigger 1-10%, reactive thinner 20-50%, wetting Agent for Printing Inks 5-25%, permeate agent 5-15%, tensio-active agent 0-2%, PH conditioning agent 0-2%, fungicidal preservative 0.1-0.5%, balance deionized water;
Wherein, the modified polyurethane resin emulsion of described UV solidification is selected from: at least one in epoxy resin-polyurethane resin emulsion, epoxy resin and acrylic ester-ester-polyurethane resin emulsion, Viscotrol C-acrylate-polyurethane resin emulsion, acrylate-polyurethane resin emulsion, organic silicon-acrylate-ester-polyurethane resin emulsion, polyester-urethane resin emulsion, polyether-polyurethane resin emulsion, polyurea-polyuretahne resin emulsion; Particle diameter <100 nanometer, 24 hours water-intake rate≤10% after film forming;
Described nano dye particle diameter <100 nanometer, comprises at least one in metalluster pigment, mineral dye, pigment dyestuff;
Described dispersion agent is organic high molecular polymer.
2. the water based ink jet ink of UV solidification according to claim 1, is characterized in that: substitute nano dye with the water-soluble dye of light fastness more than 6 grades; Water-soluble dye does not use dispersion agent when making tinting material.
3. the water based ink jet ink of UV solidification according to claim 1, is characterized in that: described organic high molecular polymer is at least one in BYK-2163, BYK-2164, BYK-180, BYK-184, BYK-190, BYK-2012, BYK-2020 dispersion agent of Bi Ke chemistry.
4. the water based ink jet ink of the UV solidification described in claim 1 or 2, is characterized in that: light trigger is bitter almond oil camphor and derivative, benzil class, alkylbenzene ketone, acyl group phosphorous oxides, benzophenone, salicylate class, two or more light trigger is composite arbitrarily for triazines.
5. the water based ink jet ink of the UV solidification described in claim 1 or 2, it is characterized in that: reactive thinner is hydroxyethyl methacrylic acid, vinylformic acid lauryl alcohol ester, vinylformic acid octadecyl, hexanediyl ester, triethylene glycol diacrylate, O-phthalic acid diethylene glycol diacrylate fat, diethylene glycol diacrylate, neopentylglycol diacrylate, tripropylene glycol diacrylate, Viscoat 295, pentaerythritol triacrylate, single, double, polyfunctionality reactive thinner is composite with 3-6:0-4:0-1.
6. the water based ink jet ink of the UV solidification described in claim 1 or 2, is characterized in that: also composite epoxy-acrylics emulsion, organosilicon modified crylic acid resin emulsion, organic fluorine modified acrylic resin emulsion, at least one in organic silicon-fluorine modified acrylic resin emulsion having UV to solidify in the modified polyurethane resin emulsion of UV solidification.
7. the water based ink jet ink of the UV solidification described in claim 1 or 2, it is characterized in that: add the auxiliary agent improving ink performance, these auxiliary agents are at least one in viscosity modifier, conductivity adjustment agent, stablizer, intercalating agent, defoamer, coupling agent, flow agent, thinner.
8. the preparation method of the water based ink jet ink of the UV solidification described in any one of claim 1-7, is characterized in that: comprise the following steps
(1) prepare each component of ink by formula, stir, grinding machinery 500-3000 rev/min of speed lapping 1-3 hour, record particulate D90≤120 nanometer in ink mixture, obtain ink mixture;
(2) ink mixture leaves standstill slaking in-7 days in 12 hours;
(3) the every physical and chemical index of ink mixture is detected according to QB/T2730.1-2005, QB/T 2730.2-2005;
(4) successively with 1 micron, 0.45 micron, 0.22 micron membrane filter filtration, finished product is obtained.
9. the application of the water based ink jet ink of the UV solidification described in claim 1 or 2, is characterized in that: be printed on without on coating media and non-print coating media, hydrophobicity and oil medium.
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| CN103087586A (en) * | 2013-01-21 | 2013-05-08 | 鲁继烈 | Waterproof and light-resistant water-based resin dye jet ink |
| CN103319953B (en) * | 2013-07-12 | 2014-09-17 | 鲁继烈 | Water-based pigment ink for quality improvement |
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| CN105017862A (en) * | 2015-07-13 | 2015-11-04 | 武汉纺织大学 | High-performance pigment ink and preparation method thereof |
| CN105017862B (en) * | 2015-07-13 | 2018-03-06 | 武汉纺织大学 | A kind of high performance pigments ink and preparation method thereof |
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Effective date of registration: 20190516 Address after: Room 511, Building B, 606 Ningliu Road, Nanjing Chemical Industrial Park, Jiangsu Province, 210000 Patentee after: Nanjing Chembridge Tech-Material Co., Ltd. Address before: 646000 No. 6, 9th floor, Dongfeng Street, Shidong Town, Longmatan District, Luzhou City, Sichuan Province Patentee before: Lu Jilie |